RU2006116444A - METHOD OF POLYMERIZATION AND REGULATION OF CHARACTERISTICS OF THE POLYMER COMPOSITION - Google Patents

METHOD OF POLYMERIZATION AND REGULATION OF CHARACTERISTICS OF THE POLYMER COMPOSITION Download PDF

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RU2006116444A
RU2006116444A RU2006116444/04A RU2006116444A RU2006116444A RU 2006116444 A RU2006116444 A RU 2006116444A RU 2006116444/04 A RU2006116444/04 A RU 2006116444/04A RU 2006116444 A RU2006116444 A RU 2006116444A RU 2006116444 A RU2006116444 A RU 2006116444A
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amount
reactor
alkane
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value
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RU2332426C2 (en
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Фред Д. ЭРМАН (US)
Фред Д. ЭРМАН
Прадип П. ШИРОДКАР (US)
Прадип П. ШИРОДКАР
Роберт Л. САНТАНА (US)
Роберт Л. САНТАНА
Портер С. ШАННОН (US)
Портер С. ШАННОН
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Юнивейшн Технолоджиз, Ллс (Us)
Юнивейшн Технолоджиз, Ллс
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged

Claims (20)

1. Способ получения полимерной композиции, обладающей целевым значением I21, включающий введение полимера с высокой молекулярной массой в полимер с низкой молекулярной массой с получением полимерной композиции в одном газофазном полимеризационном реакторе в присутствии способных к полимеризации мономеров, биметаллической каталитической композиции и по меньшей мере одного регулирующего агента, в котором регулирующий агент прибавляют в количестве, достаточном для регулирования уровня введения полимера с высокой молекулярной массой, уровня полимера с низкой молекулярной массой или их обоих, в котором газофазный полимеризационный реактор включает псевдоожиженный слой и сжижающую среду, сжижающая среда включает алкан, выбранный из группы, включающей С420алканы, и1. A method of obtaining a polymer composition having a target value of I 21 , comprising introducing a polymer with a high molecular weight into a polymer with a low molecular weight to obtain a polymer composition in one gas-phase polymerization reactor in the presence of polymerizable monomers, a bimetallic catalyst composition and at least one a regulatory agent in which a regulatory agent is added in an amount sufficient to control the level of administration of the high molecular weight polymer, match a polymer with a low molecular weight or both, wherein the gas phase polymerization reactor comprises a fluidized bed and a fluidizing medium fluidizing medium comprises an alkane selected from the group consisting of C 4 -C 20 alkanes, and в котором при увеличении содержания алкана в реакторе количество регулирующего агента увеличивается для поддержания полимерной композиции при целевом значении ее I21.in which with increasing alkane content in the reactor, the amount of the regulatory agent increases to maintain the polymer composition at its target value of I 21 . 2. Способ по п.1, в котором полимерная композиция обладает целевым значением I21, составляющим от 3 до 200 дг/мин, и в котором2. The method according to claim 1, in which the polymer composition has a target value of I 21 comprising from 3 to 200 dg / min, and in which (a) некоторое количество алкана прибавляют в реактор, и(a) some alkane is added to the reactor, and (b) некоторое количество регулирующего агента, воды или их обоих прибавляют в реактор,(b) a certain amount of a regulatory agent, water or both of them are added to the reactor, причем увеличение количества алкана приводит к необходимости введения или увеличения количества регулирующего агента, воды или их обоих, и уменьшение количество алкана приводит к необходимости удаления или уменьшения количества регулирующего агента, воды или их обоих.moreover, an increase in the amount of alkane leads to the need to introduce or increase the amount of a regulatory agent, water, or both of them, and a decrease in the amount of alkane leads to the need to remove or reduce the amount of a regulatory agent, water, or both of them. 3. Способ по п.2, в котором значение I21 составляет от 4 до 50 дг/мин,3. The method according to claim 2, in which the value of I 21 is from 4 to 50 dg / min, количество алкана составляет от 0,5 до 10 мас.% в пересчете на загрузку первичного мономера; количество воды составляет от 1 до 50 мас.ч./млн в пересчете на загрузку первичного мономера, и количество регулирующего агента составляет от 0,1 до 40 мас.ч./млн в пересчете на загрузку первичного мономера.the amount of alkane is from 0.5 to 10 wt.% in terms of the loading of the primary monomer; the amount of water is from 1 to 50 parts by weight per million based on the loading of the primary monomer, and the amount of the regulating agent is from 0.1 to 40 parts by weight per million based on the loading of the primary monomer. 4. Способ по п.1, в котором реактор эксплуатируется в режиме конденсации и алкан поступает в реактор в количестве, составляющем от 2 до 50 мас.% в пересчете на полную массу сжижающей среды.4. The method according to claim 1, in which the reactor is operated in condensation mode and alkane enters the reactor in an amount of from 2 to 50 wt.% In terms of the total mass of the fluidizing medium. 5. Способ по п.1, в котором регулирующий агент находится в туманообразном или газообразном состоянии при температуре от 50 до 120°С и давлении от 1 до 100 бар.5. The method according to claim 1, in which the regulatory agent is in a foggy or gaseous state at a temperature of from 50 to 120 ° C and a pressure of from 1 to 100 bar. 6. Способ по п.1, в котором газофазный реактор включает рецикловый трубопровод и в котором регулирующий агент прибавляют в рецикловый трубопровод ниже по потоку от теплообменника.6. The method according to claim 1, in which the gas-phase reactor includes a recycle line and in which the regulatory agent is added to the recycle line downstream of the heat exchanger. 7. Способ по п.1, в котором регулирующий агент выбран из группы, включающей спирты, простые эфиры, альдегиды, кетоны, амины, О2, монооксид углерода и их смеси.7. The method according to claim 1, wherein the regulatory agent is selected from the group consisting of alcohols, ethers, aldehydes, ketones, amines, O 2 , carbon monoxide, and mixtures thereof. 8. Способ по п.1, в котором регулирующий агент выбран из группы, включающей одноатомные C110спирты и С210простые моноэфиры, кислород и их комбинации.8. The method according to claim 1, wherein the regulatory agent is selected from the group consisting of monohydroxy C 1 -C 10 alcohols and C 2 -C 10 monoesters, oxygen, and combinations thereof. 9. Способ по п.1, в котором регулирующий агент содержится в количестве, составляющем более 1 мас.ч./млн в пересчете на загрузку первичного мономера.9. The method according to claim 1, in which the regulatory agent is contained in an amount of more than 1 parts by weight per million based on the loading of the primary monomer. 10. Способ по п.1, в котором алкилпроизводное алюминия также вводится в реактор.10. The method according to claim 1, in which the alkyl derivative of aluminum is also introduced into the reactor. 11. Способ по п.10, в котором значение I21 полимерной композиции уменьшается при увеличении количества алкилпроизводного алюминия в реакторе.11. The method according to claim 10, in which the value of I 21 of the polymer composition decreases with an increase in the amount of aluminum alkyl derivative in the reactor. 12. Способ по п.1, в котором полимерная композиция обладает целевым значением I21, составляющим от 4 до 100 дг/мин, и в котором12. The method according to claim 1, in which the polymer composition has a target value of I 21 comprising from 4 to 100 dg / min, and in which (a) некоторое количество алкана прибавляют в реактор,(a) some alkane is added to the reactor, (b) некоторое количество регулирующего агента, воды или их обоих также прибавляют в реактор, и(b) a certain amount of a regulatory agent, water, or both of them, are also added to the reactor, and (c) некоторое количество алкилпроизводного алюминия прибавляют в реактор,(c) a certain amount of an aluminum alkyl derivative is added to the reactor, причем увеличение количества алкана приводит к необходимости введения или увеличения количества регулирующего агента, воды или их обоих, и увеличение количества алкилпроизводного алюминия приводит к необходимости введения или увеличения количества регулирующего агента, воды или их обоих, так чтобы поддерживать значение I21 полимерной композиции при его целевом значении.moreover, an increase in the amount of alkane leads to the need to introduce or increase the amount of a regulating agent, water, or both of them, and an increase in the amount of an alkyl derivative of aluminum leads to the need to introduce or increase an amount of a regulating agent, water, or both of them, so as to maintain the I 21 value of the polymer composition at its target value. 13. Способ по п.12, в котором значение I21 составляет от 4 до 50 дг/мин, количество алкана составляет от 0,5 до 10 мас.% в пересчете на загрузку первичного мономера, количество воды составляет от 1 до 50 мас.ч./млн в пересчете на загрузку первичного мономера, количество регулирующего агента составляет от 0,1 до 40 мас.ч./млн в пересчете на загрузку первичного мономера, и количество алкилпроизводного алюминия составляет от 50 до 200 мас.ч./млн в пересчете на загрузку первичного мономера.13. The method according to item 12, in which the value of I 21 is from 4 to 50 dg / min, the amount of alkane is from 0.5 to 10 wt.% In terms of the loading of the primary monomer, the amount of water is from 1 to 50 wt. hours / million in terms of the loading of the primary monomer, the amount of regulatory agent is from 0.1 to 40 parts by weight / million in terms of the loading of the primary monomer, and the amount of alkyl derivative of aluminum is from 50 to 200 parts / million in in terms of the loading of the primary monomer. 14. Способ по п.1, в котором при введении алкана или увеличении его вводимого количества от 0,5 до 10 мас.% в пересчете на загрузку первичного мономера значение I21 уменьшается на 2-50%, если вводимое в полимеризационный реактор количество алкилпроизводного алюминия, регулирующего агента и воды остается постоянным.14. The method according to claim 1, in which when the alkane is introduced or its input amount is increased from 0.5 to 10 wt.%, Calculated on the loading of the primary monomer, the value of I 21 decreases by 2-50% if the amount of the alkyl derivative introduced into the polymerization reactor aluminum regulating agent and water remains constant. 15. Способ по п.1, в котором при введении алкана или увеличении его вводимого количества от 1 до 6 мас.% в пересчете на загрузку первичного мономера значение I21 уменьшается на 2-50%, если вводимое в полимеризационный реактор количество алкилпроизводного алюминия, регулирующего агента и воды остается постоянным.15. The method according to claim 1, in which when the alkane is introduced or its input amount is increased from 1 to 6 wt.% In terms of the loading of the primary monomer, the value of I 21 decreases by 2-50% if the amount of the aluminum derivative introduced into the polymerization reactor, regulatory agent and water remains constant. 16. Способ по п.1, в котором биметаллическая каталитическая композиция включает подложку из неорганического оксида, металлоцен и содержащие титан и магний катализаторы Циглера-Натта.16. The method according to claim 1, wherein the bimetallic catalyst composition comprises an inorganic oxide support, a metallocene, and Ziegler-Natta catalysts containing titanium and magnesium. 17. Способ по п.1, в котором способные к полимеризации мономеры представляют собой этилен и олефин, выбранный из числа С310α-олефинов.17. The method according to claim 1, wherein the polymerizable monomers are ethylene and an olefin selected from among C 3 -C 10 α-olefins. 18. Способ по п.1, в котором газофазный полимеризационный реактор эксплуатируется при температуре от меньшей температуры плавления полимерной композиции до превышающей 50°С.18. The method according to claim 1, in which the gas-phase polymerization reactor is operated at a temperature from a lower melting temperature of the polymer composition to above 50 ° C. 19. Способ по п.1, в котором мономеры, алкилпроизводное алюминия и алкан в количестве, составляющем от 1 до 10 мас.% в пересчете на поток первичного мономера, прибавляют в полимеризационный реактор с получением полимерной композиции, обладающей значением I21, равным А, с последующим введением регулирующего агента в количестве, составляющем от 0,1 до 100 ч./млн в пересчете на скорость потока первичного мономера, и необязательно воды в количестве, составляющем от 1 до 50 ч./млн в пересчете на загрузку первичного мономера в полимеризационный реактор, для получения полимерной композиции, обладающей значением индекса текучести, равным В, в котором значение А меньше значения В на величину, составляющую более 2 дг/мин в значении I21.19. The method according to claim 1, in which the monomers, the alkyl derivative of aluminum and alkane in an amount of from 1 to 10 wt.% In terms of the flow of the primary monomer, are added to the polymerization reactor to obtain a polymer composition having an I 21 value of A , followed by the introduction of a regulatory agent in an amount of from 0.1 to 100 ppm in terms of the flow rate of the primary monomer, and optionally water in an amount of from 1 to 50 ppm in terms of the loading of the primary monomer polymerization reactor, for preparing a resin composition having a flow index value equal to B, wherein the value A is smaller than the value B by an amount greater than 2 dg / min I 21 value. 20. Способ по п.1, в котором мономеры, водород, алкилпроизводное алюминия и алкан в количестве, составляющем от 1 до 10 мас.% в пересчете на поток первичного мономера, прибавляют в полимеризационный реактор с получением полимерной композиции, обладающей значением I21, равным А, с последующим введением непрерывного количества регулирующего агента в количестве, составляющем от 0,1 до 50 ч./млн в пересчете на поток первичного мономера, и необязательно воды в количестве, составляющем от 1 до 50 ч./млн в пересчете на загрузку первичного мономера в полимеризационный реактор, введение регулирующего агента и необязательно воды проводят в рецикловый трубопровод выше по потоку от теплообменника полимеризационного реактора, для получения полимерной композиции, обладающей значением индекса текучести, равным В, в котором значение А меньше значения В на величину, составляющую более 2 дг/мин в значении I21.20. The method according to claim 1, in which the monomers, hydrogen, an alkyl derivative of aluminum and alkane in an amount of from 1 to 10 wt.% In terms of the flow of the primary monomer, are added to the polymerization reactor to obtain a polymer composition having a value of I 21 , equal to A, followed by the introduction of a continuous amount of a regulatory agent in an amount of from 0.1 to 50 ppm in terms of the flow of the primary monomer, and optionally water in an amount of from 1 to 50 ppm in terms of loading primary monomer to polymer an isolation reactor, the introduction of a regulatory agent and optionally water is carried out in a recycle line upstream of the heat exchanger of the polymerization reactor to obtain a polymer composition having a yield index of B, in which A is less than B by more than 2 dg / min in the meaning of I 21 .
RU2006116444/04A 2003-10-15 2004-03-25 Method of polymerisation and regulation of characteristics of polymeric composition RU2332426C2 (en)

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